Exploring the Interaction of Water with Open Metal Sites in MIL-101(Cr) by 1H NMR Relaxometry and ReaxFF Molecular Dynamics Simulations | Sciact - CRIS-system of Boreskov Institute of Catalysis

Exploring the Interaction of Water with Open Metal Sites in MIL-101(Cr) by 1H NMR Relaxometry and ReaxFF Molecular Dynamics Simulations Full article

Journal

The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455

Output data

Year: 2023, Volume: 127, Number: 36, Pages: 17851-17862 Pages count : 12 DOI: 10.1021/acs.jpcc.3c03901

Tags

ORGANIC FRAMEWORK; NUCLEAR-RELAXATION; ADSORPTION; REMOVAL; LIQUIDS; FUELS

Authors

Martini Francesca ^1,2,3 , Calucci Lucia ^2,3 , Gordeeva Larisa G. ⁴ , Monti Susanna ³ , Solovyeva Marina V. ⁴ , Trouki Cheherazade ^5,6 , Pizzanelli Silvia ^2,3

Affiliations

1	Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via G. Moruzzi 13, 56124 Pisa, Italy
2	Centro per l’Integrazione della Strumentazione Scientifica dell’Università di Pisa (CISUP) Lungarno Pacinotti 43/44, 56126 Pisa, Italy
3	Istituto di Chimica dei Composti OrganoMetallici, Consiglio Nazionale delle Ricerche─CNR, Via G. Moruzzi 1, 56124 Pisa, Italy
4	Boreskov Institute of Catalysis, Ac. Lavrentiev av. 5, Novosibirsk 630090, Russia
5	Istituto per i Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche─CNR, Via G. Moruzzi 1, 56124 Pisa, Italy
6	Dipartimento di Farmacia, Università di Pisa, Via Bonanno 6, 56126 Pisa, Italy

Funding (1)

University of Pisa

PRA_2022_34

In this work, we investigated the state of water in the metal–organic framework MIL-101(Cr) by combining 1H magic angle spinning (MAS) NMR, NMR relaxometry, and molecular dynamics (MD) simulations based on a reactive force field. The MD simulations indicated that water molecules are coordinated to the open metal sites and are organized in shells. Through 1H T2 and T1 relaxation measurements at the fixed Larmor frequency of 21 MHz, water in the intergrain spaces was distinguished from that in the intragrain mesopores of MIL-101(Cr). 1H MAS NMR measurements showed that water in the mesopores is structurally ordered, as revealed by the presence of 1H–1H residual dipolar interaction. The 1H NMR relaxometric behavior of water located in the intergrain spaces of MIL-101(Cr) as a function of the magnetic field strength, determined by fast field cycling NMR relaxometry, was interpreted extending an existing model, generally applied to paramagnetic aqua ions in solution, to the case of Cr3+ ions fixed on the surface of the metal–organic framework. The model predicts the exchange of water between the first and second shell of a Cr3+ ion, giving access to the water residence time in the first shell that would be difficult to determine using other techniques. In the temperature interval of 25–70 °C, water residence times in the range of tens of nanoseconds were found and a limited accessibility of water to the open metal sites located on the external grain surface was observed.

Martini F. , Calucci L. , Gordeeva L.G. , Monti S. , Solovyeva M.V. , Trouki C. , Pizzanelli S.
Exploring the Interaction of Water with Open Metal Sites in MIL-101(Cr) by 1H NMR Relaxometry and ReaxFF Molecular Dynamics Simulations
The Journal of Physical Chemistry C. 2023. V.127. N36. P.17851-17862. DOI: 10.1021/acs.jpcc.3c03901 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Jun 9, 2023
Accepted:	Aug 19, 2023
Published online:	Sep 1, 2023
Published print:	Sep 14, 2023

Web of science:	WOS:001061000600001
Scopus:	2-s2.0-85171748210
Elibrary:	54975722
Chemical Abstracts:	2023:1805593
Chemical Abstracts (print):	184:186178
OpenAlex:	W4386365324

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